Monoazo compounds containing a substituted phthalimide diazo component

ABSTRACT

MONOAZO DYESTUFFS WHICH ARE FREE FROM SULPHONIC ACID GROUPS AND CORRESPOND TO THE GENERAL FORMULA   1,3-DI(O=),2-((X)N,(R1)M-PHENYL),(K-N=N-),(R)M-ISOINDOLINE   IN WHICH K DENOTES THE RADICAL OF A MONOFUNCTIONAL COUPLING COMPONENT; R AND R1 STAND FOR IDENTICAL OR DIFFERENT SUBSTITUENTS; X MEANS AN OPTIONALLY SUBSTITUTED CARBOXYLIC ACID HYDRAZIDE GROUP; M STANDS FOR AN INTEGER FROM 0 TO 3; AND N STANDS FOR THE NUMBERS 1 OR 2, AS WELL AS PROCESSES FOR THEIR PRODUCTION AND THEIR USE AS PIGMENT DYSTUFFS.

United States Patent Ice 3,743,632 MONOAZO COMPOUNDS CONTAINING A SUB- STITUTED PHTHALIMIDE DIAZO COMPONENT Walter Horstmann, Cologne, and Edgar Siege], Leverkusen, Germany, assiguors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Aug. 28, 1970, Ser. No. 67,975 Claims priority, application Germany, Sept. 3, 1969, P 44 702.0 Int. Cl. C09b 29/20, 29/32, 29/38 U.S. Cl. 260-152 Claims ABSTRACT OF THE DISCLOSURE Monoazo dyestuffs which are free from sulphonic acid groups and correspond to the general formula 0 i E KN=N N in which K denotes the radical of a monofunctional coupling component; R and R stand for identical or difierent substituents; X means an optionally substituted carboxylic acid hydrazide group; m stands for an integer from 0 to 3; and n stands for the numbers 1 or 2, as well as processes for their production and their use as pigment dyestulfs.

The subject-matter of the present invention comprises valuable new monoazo dyestuffs which are free from sulphonic acid groups and correspond to the general formula R u 1) M in which K denotes the racial of a monofunctional coupling components; R and R stand for identical or difierent substituents; X means an optionally substituted carboxylic acid hydrazide group; m stands for an integer from 0 to 3; and it stands for the numbers 1 or 2, as well as processes for their production and their use as pigment dyestuffs.

Suitable radicals X are, for example, carboxylic acid hydrazide radicals which are substituted by acyl, alkyl, aralkyl or aryl radicals.

Suitable acyl radicals are, for example, alkylcarbonyl, arylcarbonyl, especially phenylcarbonyl or phthaloyl radicals which may be substituted by lower alkoxy groups, lower alkyl groups, phenyl groups, halogen, nitro or alkylcarbonyl-amino groups; and also cycloalkylcarbonyl radicals.

Suitable alkyl radicals are primarily those with 1-4 carbon atoms.

Suitable aralkyl radicals are primarily benzyl radicals which may be substituted by halogen, nitro, alkyl or alkoxy radicals.

Suitable aryl radicals are primarily phenyl radicals which may be substituted by halogen, nitro, alkyl or alkoxy groups. I

Suitable radicals X are, for example:

3,743,632 Patented July 3, 1973 Suitable radicals K are primarily the radicals of 2-hydroxy-naphthoie acid (3) arylides, acetoacetic acid arylides, pyrazolones-(S) and S-amino-pyrazoles.

Preferred dyestufi's are those of the general formula 1): (X011 K|N=N Y (H) in which K stands for the radical of a Z-hydroxy-naphthoic acid-(3)-ary1ide, acetoacetic acid arylide, pyrazolone-(S) or 5-aminopyrazole; R m and n have the same meaning as above; and X stands for a carboxylic acid hydrazide group substituted by acyl, alkyl, aralkyl or aryl radicals, especially those of the formula (R m )x F (xi)n I in which B X K, m and n have the same meaning as above.

The new azo dyestuffs of the Formula I are obtained by reacting azo compounds of the formula 00011 K N=N (R m (IV) in which K, R and m have the same meaning as above, or their functional derivatives, such as anhydrides, semiesters or nueral esters, with compounds of the formula (X) in which R X, m and n have the same meaning as above, in a molar ratio of about 1:1, optionally in the presence of suitable condensation agents, in a high-boiling organic solvent, the components being so chosen that the final dyestuffs are free from sulphonic acid groups.

A group of particularly valuable dyestuffs within the scope of the products of the Formula I are obtained by .4 in which R, R X, m and n have the same meaning as above, are diazotised in the usual way and the diazo compound is coupled with coupling components KH.

The compounds of the Furmula VIII are obtained by the reaction of optionally substituted 3- and 4-nitrophthalic acids or their functional derivatives with compounds of the Formula V in a high-boiling organic solvent in the presence of acidic condensation agents and subsequent reduction of the resultant nitro compounds.

The starting dyestuifs of the Formulae IV and VI are obtained in the usual way by diazotising the optionally substituted amino-phthalic acids or their functional derivatives and coupling with monofunctional coupling components. The following diazo components can be used for this purpose, for example:

acid,

Suitable monofunctional coupling components K-H are, for example:

Z-hydroxy-naphthoic acid- (3 -anilide,

2-hydroxy-naphthoic acid- 3 -2'-methyl-anilide,

Z-hydrOXy-naphthoic acid- 3 -amide,

Lhydroxy-naphthoic acid- 3 4-methyl) -anilide,

2-hydroxy-naphthoic acid- 3 2'-methoxy) -anilide,

Z-hydroxy-naphthoic acid- 3 4'-methoxy) -anilide,

2-hydroxy-naphthoic acid- (3 (3 '-nitro) -anilide,

Z-hydroxy-naphthoic acid- (3 2,4'-dimethyl)-anilide,

2-hydroxy-naphthoic acid- (3 (2'-methyl-5- chloro) anilide,

Z-hydroxy-naphthoic acid-( 3 4-chloro) -anilide,

2-hydroxy-naphthoic acid- 3 (2,5 -dimethoxy-4'- chloro )-ar1ilide,

2-hydroxy-naphthoic acid- (3 -(2,4'-dimeth0xy-5- chloro -anilide,

Z-hydroxy-naphthoic acid- (3 (2-methyl-4'- chloro) anilide,

Z-hydroxy-naphthoic acid-'( 3 (Z'methoxy- '-chloro anilide,

2-hydroxy-naphthoic acid- (3 (2'-methyl-3 chloro) anilide,

2-hydroxy-naphthoic acid- (3 [naphthyl-( 1') ]-amide,

Z-hydroxy-naphthoic acid- 3 [naphthyl- (2) -amide,

2-hydroxy-naphthoic acid- (3 (2-ethoxy) -anilide,

2-hydroxy-naphthoic acid- 3 (4'-ethoxy) -anilide,

2-hydroxy-naphthoic acid-( 3 (2'-methoxy-5 methyl) -anilide,

Z-hydroxy-naphthoic acid- 3 (4-acetylamino anilide,

5- (2,3'-hydroxy-naphthoylamino -benzimidazolone,

1-phenyl-3-methyl-pyrazolone- (5 1- (4-chlorophenyl) -3-methyl-pyrazolone-(5 1- (3 '-nitro-phenyl) -3 -methyl-pyrazolone-(5 1- (2'-chlorophenyl) -3-methyl-pyrazolone- (5 l-phenyl-pyrazolone- 5 -carboxylic acid- 3 -amide,

l-phenylpyrazolone- S -carb oxylic acid- (3 -methyl ester,

l-phenyl-3-methyl-S-aminopyrazole;

acetoacetic acid anilide,

acetoacetic acid-Z-chloro-anilide,

acetoacetic acid-2,4-dimethyl-anilide,

acetoacetic acid-Z-methyl-am'lide,

The condensation of the azo compounds (IV) or (V1) with compounds of the type (V) according to the invention is preferably carried out in a high-boiling organic solvent and in the presence of dehydrating agents. The condensation is carried out, for example, at an elevated temperature, generally in the range from 80 C. to 240 C. and preferably between 100 C. and 180 C., possibly under pressure.

Compounds (V) which are suitable for the preparation of the azo dyestuffs of the Formula I are, for example:

N-phenyl-N- (4-amino-benzoyl) -hydrazine,

N-methyl-N-(4-amino-benzoyl)-hydrazine,

N -acetyl-N- (4-amino-benzoyl)-hydrazine,

N-acetyl-N- 3-amino-benzoyl) -hydrazine,

N benzoyl-N (4-amino-benzoyl)-hydrazine,

N- (4-chlorobenzoyl)-N'-(4-amino-benzoy1)- hydrazine,

N- (4-methy1-benzoyl) -N- (4-amino-benzoyl) hydrazine,

N- 2,5-dichloro-benzoyl) -N- (4-amino-benzoyl) hydrazine,

N-(2,3,4,5-tetrachloro-benzoyl)-N'- (4-amino-benzoyl)- hydrazine,

N-cyclo-hexanyl-N'- (4-amino-benzoyl) -hydrazine,

Condensation agents preferably to be added are, for example: acidic dehydrating agents such as formic acid, acetic acid, propionic acid, anhydrous sodium acetate, ptoluenesulphonic acid.

Particularly valuable condensation agents are acetic acid, propionic acid and mixtures thereof.

The reaction of the compounds (IV) and (VI) or of their derivatives with the compounds (V) is carried out in a molar ratio of about 1:1, preferably with an excess of 5 to 20% of the component (V), in order to achieve complete conversion.

The products which can be obtained according to the invention are valuable new pigment dyestuffs which are generally characterised by good fastness to light, solvents and migration as well as by good thermal stability in a variety of substrates. They are used for the colouring of papers, lacquers and synthetic materials, such as e.g. plasticiser-containing polyvinyl chloride, polyethylene and coor graft-polymers of acrylonitrile-butadiene-styrene, and for the preparation of pigment pastes and printing colours.

In the following examples the temperatures are given in degrees centigrade.

EXAMPLE 1 10 g. of the azo dyestutf obtained from diazotised 3- amino-phthalic acid and Z-hydroxy-naphthoic acid-(3)- (4'-ethoxy)-anilide are heated in a mixture of 200 g. odichlorobenzene and 20 g. glacial acetic acid at 110 C. for 30 minutes. 6.8 g. N-(2,5-dichlorobenzoyl)-N-(4 amino-benzoyl)hydrazine are then added, the mixture is heated at 110120 C. for 10 hours, the product is filtered 01f with suction at 100 C., washed with hot o-dichlorobenzene and then with cold methanol, each time until the runnings are clear, and dried at in a vacuum. The yield amounts to 13.6 g. of a red pigment dyestutf of the formula mam-Q-nn-oo on N- [naphthoyl-( 2) ]-N- (4-amino-benzoyD-hydrazine, N-(4-amino-benzoyl)-amino-phthalimide, 50 N-(3-amino-benzoyl)-amino-phthalimide,

N- (4-amino-benzoy1)-amino-3-acetamino-phthalimide, N-(4-amino-benzoyl)-amino-4-acetamino-phthalimide, 3,5-bis- (N -benzoyl-carbazinyl)-aniline.

which is fast to lacquer-coating and very fast to light.

EXAMPLE 2 9.7 g. of the azo dyestufl obtained from diazotised 3- amino-phthalic acid and 2-hydroxy-naphthoic acid-(3)- (4'-methoxy)-anilide are heated in a mixture of 200 g. chlorobenzene and 20 g. glacial acetic acid at C. for 1 hour, 5.8 g. N-(4-amino-benzyl)-amino-phthalimide are then added, the mixture is heated at 110-120 C. for a further 5 hours, the precipitated pigment is filtered oil? with suction at 100, washed with 200 m1. of hot chlorobenzene and ml. of cold methanol, and dried at 50 until the weight remains constant.

7 There are obtained 13.5 g. of a red pigment dyestulf of the formula which is fast to lacquer-coating.

3,743,632 7 EXAMPLE 3 9.1 g. of the azo dyestuif obtained from diazotised 3- amino-phthalic acid and Z-hydroxy-naphthoic acid-(3)- anilide are heated in a mixture of 200 g. o-dichloroben- 8 We claim: 1. A monoazo pigment dyestufl? free from sulfonic acid groups having the formula zene and 20 g. glacial acetic acid at 100 for 30 minutes, 5 1)! (X) 6.0 g. N-(4-chloro-3-amino-benzoyl)-N-(benzoyl)-hydrazine are then added, the mixture is heated at 120 for 10 hours, the product is filtered ofl? with suction at 100,

washed with hot o-dichlorobenzene and cold methanol, 10 (R m each time until the runnings are clear, and dried in a vacuum at 50. The yield amounts to 13.4 g. of a red pigment dyestufi of the formula K is the radical of a monofunctional coupling component selected from the group consisting of 2-hydroxynaphthoic-acid-(3)-ary1ide, acetoacetic acid arylide, pyrazolone-(S) and S-amino-pyrazole;

R and R are identical or different members selected from the group consisting of C -C -alkyl; trifiuoromethyl; halogen; C -C -a1koxy and nitro;

X is hydrazine-carbonyl; or hydrazino carbonyl substituted in the N-atom distal to the carbonyl with a Diazo component Coupling component imidation component Shade 3-anilinophthallc Z-hydroxy-naphthoicacid -an1llde N-acetyl-N'-(4-axnlno-benzoyl)-hydrazine Red.

do N-benzoylN-(4-amino-benzoyl)hydrazine Red. d N-(4-ehlorobenzyol)-N-(d-amlno-benzoyD-hydrazin Red. do N-(2,5-dichlorobenzoy1)-N'-(tamino-benzoyD-hydrazine Red. do N-(4-amlno-benzoyl)-amlno-phthalimide Red. Z-hydroxy-naphthoic acid-(3)-(2-rnethyl)-anil.ide N-benzoyl-N-(4-amino-benzoyD-hydrazine Red. do N-(2,5-dichlorobenzoyl)-N-(4amino-benzo Red. do 3,fi-bis-(N -benzoyl-carbazlnyl)-aniline Red. Z-hydroxy-naphthoic aeid-(3)-(4-ch10ro)-anillde N-benzoyl-N-(4-amlno-benzoyD-hydrazin Red. N-(4-chlorobenzoyl)-N-(4-amino-benzoyl)-h Red. do N-(d-amino-benzoyl)-amino-phthalimide Red. do 3,5-bl s-[N -(4-chlorobenzoyl)-carbazinyl]-anil1n Red. Z-hydroxy-naphtholc acid-(3)-(3-nitro)-an11ide N-(4-chlorobenzoyl)-N-(4-an1lno-benzoyl)-hydrazln Red. do N-(2,3,4,6-tetrachlorobenzoyl)-N-(4-aminobenzoyD-hydrazine Red. Z-lgdroarfiggpithoic aeid-(3)-(2-methyl-4-me- N -aeety1-N-(4-amino-benzoyD-hydrazme Bordeaux:

oxy 1 e. do N-benzoyl-N-(4-amino-benzoyl)-hydrazine Do. do N-(2,5-dicl1lorobenzoyl)-N'-(4-amionbenzoyD-hydrazine Do. Z-hydrgvxy-naphthoic aeid-(3)-[naphthy1-(1)]- N-benzoylN-(4-amino-benzoyl)-hydrazine Red.

am e.

do N-(2,fi-dlchlorobenzoyl)-N-(4-amino-benzoyl)-hydrazine Red. do N-(4-amino-benzoy1)-aminophtha1imide Red. Z-hydroxy-naphthoic acid-(3)-[napl1thyl-(2)]-amido do Red. do 3,5-bis-[N -(4-ehlorobenzoy1)carbazinyl]-anil.ine Red. do N-(2,3,4,5-tetrachlotobenzoyl)-N-(4-eminobenzoy1)-hydrazine.. Red. 2-hydroxy-naphthoic acld-(3)-(2-ethoxy)- do Red. do N-benzoy1-N-(4-amino-benzo l)-hydrazine Red. Z-hydroxy-naphthoio acid (3)-(4-eth0xy)anilide. N -acetyl-N- 4-amino-benzoyl hydrazine..- Red. do N-benzoyl-N -(4-amino-benzoyl)-hydrazine Red. do N-(2,3,4,5-tetrachlorobenzoyl)-N-(4-amino-benzoyD-hydrezine.- Red.- do 3,5-bis-(N -benzoyl-carbazinyD-aniline Red. do N-(4-amino-benzoyD-aminophthalimide Red. Z-hydroxy-naphthoic acid (3)-(4' -II16i7hOXy)-m1ilifln do Red. do N-benzoyl-N-(4-amino-benzoy1)-hydrazine Red. do N-(Hhlorobenzoyl)-N-(4-aminobenzoyl)-hydrazine. Red: do N-( t-chlorobenzoyl)-N-(3-aminobenzoy1)-hydrazine Red. do N-(4-ch1orobenzoyl)-N-(3- 'no-4-eh1oro-benzoy1)-hydraz1ne. Red. Aceotaeetic acid-2,6-dimethoxy-4-ehloro-anilide N-benzoyl-N-(4-amino-benz0yl)-hydrazine Yellow.

do N-(2,5-dich1orobenzoyl)-N- 4-am1nobenzoyl)-hydrazine Do. 0-- do N-(4-amino-benzoyl)-aminophthalimide Do. 4-8.1]Il1'10phi7hali0 Z-hydroxy-naphthoic aeid-(3)-anillde N-benzoyl-N-(3-aminobenzoyl)-hydrazine..- Red.

Dodo N-benzoyl-N'-(4-amlno-benzo l)-hydrazine Red. Do do 3,5-bis-(N benzoyl-ca.rbazinyl -aniline Red. 4-amit11i1o-5- 2-hydroxy-naphthoie acid-(3)-(4-ethoxy)- i do Red;

me oxyphthalic acid.

Do. do o N-benzoyl-N'-(4-amino-benzoyl)-hydrazine Red. Do d N-(2,3,4,fi-tetrechlorobenzoyl)-N'-(4-amino-benzoyl)-hydrazlne Red.

X is hydrazino-carbonyl; or hydrazine carbonyl submember selected from the group consisting of C -C alkyl; phenyl; benzyl; phenyl or benzyl substituted with halogen, nitro, C C -alkyl or C -C -alkoxy; C -C -alkyl-carbonyl; naphthylcarbonyl; cyclohexylcarbonyl; diphenylcarbonyl; phenylcarbonyl; benzylcarbonyl; phenyl or benzylcarbonyl substituted in the phenyl nucleus with halogen, nitro, C -C -alkyl; or C C -alkoxy; phthaloyl; or phthaloyl substituted in the phenyl nucleus with C C -alkyl, C -C -alkoxy, phenyl, halogen, nitro, or C C -alkyl carbonyl amino; m is an integer from to 3; and n is 1 0r 2.

stituted in the N-atom distal to the carbonyl with a member selected from the group consisting of C -C alkyl; phenyl; benzyl; phenyl or :benzyl substituted with chloro, nitro, C -C -alkyl or methoxy; C -C alkyl-carbonyl; naphthylearbonyl; cyclohexylcarbonyl; diphenylcarbonyl; phenylcarbonyl; benzylcarbonyl; phenyl or benzyl carbonyl substituted in the phenyl nucleus with chloro, nitro, C -C -alkyl; or methoxy; phthaloyl; or phthaloyl substituted in the phenyl nucleus with C C -alkyl, C -C alkoxy, phenyl,

2. The monoazo dyestufi of claim "1 in which the radical K is 2-hydroxy-naphthoic acid-(3)-arylide.

3. The monoazo dyestufi of claim 1 of the formula chloro, nitro or C -C -a1kyl carbonyl amino; m is an integer from 0 t0 3; and n is 1 or 2.

K N=N o References Cited (an X UNITED STATES PATENTS 3,454,550 7/1969 Newland 260-152 U 3,526,618 9/1970 Horstmann et a1. 260152 3,551,407 12/1970 Dehnert et al. 260152 3,591,324 7/1971 Dehnert et a1 260-152 4. The monoazo dyestuff of claim 1 in which LEWIS GOTTS Pmnary Examiner "R and R are the same or different members selected C F, WARREN, Assistant E i from the group consisting of C -C -alkyl; trifluoromethyl; fiuoro; chloro; bromo; methoxy; ethoxy; and US. Cl. X.R.

nitro; 260-162, 326 A UNirED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. i 3 17431632 Dated July 3, 1973 hwentm-(s) Walter Hor-stmann'et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

' Column 2, line 53 "-co CH should read co-cn Column 3, line 26, "B," should read R o 1 Column 3, line 32, "K N=N" should read ---KN=N- Column 3, line 37, "nueral" should read -neutral- Column 4, line 4, "Furmula" should read --Formula-- Column 4, line 40, After line 40 insert the following two I sentences 2-hydroxy-naphthoio acid-(3)-(2'-chloro)-an1l1de, 2hydroxy-naphthoic acid(3)-(4'chloro)-anilide,

Column 4, line 44, after -(3)--(" insert the following Column'4, line 49, -chloro" should read i-methoxy Signed and sealed this lOth day of. December 1974.

(FEAL) J I Attest:

MCCOY GIBSON JR. c". MARSHALL DANN Arresting Officer v Commissioner of Patents 

